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Rechargeable Batteries: History, Progress, and Applications Rajender Boddula
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Library of Congress Cataloging-in-Publication Data
ISBN 978-1-119-66189-4
Cover image: Pixabay.com
Cover design by Russell Richardson
Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines
Printed in the USA
10 9 8 7 6 5 4 3 2 1
G. Ranjith Kumar, K. Chandra Babu Naidu, D. Baba Basha, D. Prakash Babu, M.S.S.R.K.N. Sarma, Ramyakrishna Pothu, and Rajender Boddula
2.5
2.6
4
3.4
3.5
3.6
5
S. Ramesh, K. Chandrababu Naidu, K. Venkata Ratnam, H. Manjunatha, D. Baba Basha and A. Mallikarjauna
4.1
4.2
Praveen Kumar Yadav, Sapna Raghav, Jyoti Raghav and S. S. Swarupa
5.1
5.2
5.2.2.2
Muhammad Mudassir Hassan, Muhammad Inam Khan, Abdur Rahim and Nawshad Muhammad
6.1
6.2
7.2
7.3
7.4 Electrochemical Specifications of Activated Carbon as a Cathode 92
7.4.1 Electrochemical Evaluation of Cathode Substances La1−XCaxCoO3 Zinc
7.5 Extremely Durable and Inexpensive Cathode Air Catalyst 93
7.5.1 Co3O4/Mno2 NPs Dual Oxygen Catalyst as Cathode for Zn-Air Rechargeable Battery 94
7.5.2 Carbon Nanotubes (CNT) Employing Nitrogen as Catalyst in the Zinc/Air Battery System 94
7.5.3 Magnesium Oxide NPs Modified Catalyst for the Use of Air Electrodes in Zn/Air Batteries 94
7.5.4 Silver-Magnesium Oxide Nanocatalysts as Cathode for Zn-Air Batteries 95
7.5.5 One-Step Preparation of C-N Ni/Co-Doped Nanotube Hybrid as Outstanding Cathode Catalysts for Zinc-Air Batteries 95
viii Contents
7.6 Hierarchical Co3O4 Nano-Micro Array With Superior Working Characteristics Using Cathode Ray on Pliable and Rechargeable Battery
7.7 Dual Function Oxygen Catalyst Upon Active Iron-Based Zn-Air Rechargeable Batteries
7.7.1 Co4N and NC Fiber Coupling Connected to a Free-Acting Binary Cathode for Strong, Efficient, and Pliable
8
8.2.4
8.2.5
8.3
9 Safety and Environmental Impacts of
Saurabh Sharma, Abhishek Anand, Amritanshu Shukla and Atul Sharma
9.1
9.2 Working Principle of Zinc-Based Batteries
9.2.3
12
Contents 11.5.4
13 Security, Storage, Handling, Influences and Disposal/Recycling
ManjuYadav and Dinesh Kumar 13.1
Preface
The growing demand for electric energy storage has prompted many researchers to pursue advanced replacement batteries. Zinc-ion batteries have attracted widespread attention as a viable alternative to the lithium-ion batteries that dominate the market. Zinc is the 4th most abundant metal in the world, which can help to increase the popularity of electric vehicles (EVs) by diminishing the cost of the vehicles. Theoretically, a zinc battery possesses five times the energy density of a lithium battery. Primary Zn-air batteries were first introduced and commercialized in the 1930s. Since then, companies like Evercel, Fluidic Energy, Z-Power, EOS, Zinc Five, ZnR Batteries, ZAF, Zinium, etc., have patented and commercialized zinc-based battery solutions. However, Fluidic energy is currently producing reversible Zn-air technology. Zn-based batteries are preferred among all other metal-air batteries because of their salient features like low cost, lightweight, scale up, high energy density, safer battery technology, and environmental friendliness. These rechargeable batteries are very important rising energy storage systems because of their usability in portable electronic devices, grid management, and electric vehicles.
Zinc Batteries: Basics, Developments, and Applications is intended as a discussion of the different zinc batteries for energy storage applications. It also provides an in-depth description of various energy storage materials for Zn batteries. This book is an invaluable reference guide for electrochemists, chemical engineers, students, faculty, and R&D professionals in energy storage science, material science, and renewable energy. Based on thematic topics, the book contains the following fourteen chapters:
Chapter 1 details the various types of carbon structures used for the development of the zinc-ion battery (ZB). The major focus is on the ultimate
xiv Preface
design of ZBs using carbon to enhance oxygen reduction reaction for the better performance of ZBs.
Chapter 2 elucidates the different zinc batteries for energy-storage applications. The structure of a zinc battery is discussed. Also, the anode and cathode materials of zinc-carbon, zinc-cerium, and zinc–bromine batteries are highlighted for energy storage applications.
Chapter 3 discusses the fundamentals of zinc batteries and their scope of improvement by presence of metal additives like nickel and cobalt to prepare them as futurist batteries on a large scale. It focuses on their working, advantages and disadvantages, and the outlook and prospects of metal additives–based zinc batteries.
Chapter 4 focuses on how manganese-based material for Zn batteries will exhibit extensive properties for future use.
Chapter 5 discusses the different types of electrolytes, such as aqueous, nonaqueous, solid polymer and biopolymer electrolytes that are used in Zn-ion batteries. Additionally, it also highlights the different types of advancements in the electrolytes and recently reported electrolytes for the Zn-ion batteries.
Chapter 6 discusses zinc-ion batteries, their types and storage mechanisms. Several anodes for zinc-ion batteries with different morphologies and nanostructures are discussed and analyzed. A glimpse of the future of zinc-ion batteries is also discussed.
Chapter 7 discusses the cathode materials for zinc-air batteries. It also discusses the cathode definition, zinc cathode structure, non-valuable materials for cathode electrocatalytic, electrochemical specifications of activated carbon as a cathode, electrochemical evaluation of cathode substances La1-xCaxCoO3 zinc batteries and introduction of the other important synthesized cathode for zinc-air batteries.
Chapter 8 provides an up-to-date overview of research efforts on various zinc anode coatings to improve the stability of the charging cycle and design a new and improved zinc anode for increasing the battery energy
Preface xv
efficiency and its lifetime. The challenges and problems facing zinc anodes of electrically rechargeable zinc-air batteries are discussed.
Chapter 9 discusses the basic principle and types of zinc-based batteries, along with their environmental effects. A detail discussion is presented on safety-related issues. Further, disposal and recycling methods are also highlighted.
Chapter 10 overviews the basic principles and developments of zinc-air batteries. This chapter elaborates on the public specifications, zinc-air electrode chemical reaction, zinc/air battery construction, primary Zn/ Air Batteries, principles of configuration and operation of Zn/air batteries, developments in electrical fuel Zn/Air batteries and Zn/air versus metal/ air systems.
Chapter 11 covers the widespread study of the history and advancements identified with Zinc batteries. Further, challenges confronting the advancement of new Zinc batteries are featured, along with future research viewpoints.
Chapter 12 discusses the effects of electrolyte selection, different electrolyte types, and anode selection on the inherent characteristics of the electrolyte, in rechargeable zinc-air batteries. Broad categories of electrolytes, e.g., acidic or alkaline electrolytes, polymers, and ionic liquids are investigated in this chapter with focus on the performance enhancement of zinc batteries by the proper electrolyte selection.
Chapter 13 overviews different issues associated with the zinc electrode. Safety, storage, handling, influences and disposal/recycling of zinc batteries are also discussed. The primary focus is given on the impacts on the ecological system.
Chapter 14 deals with the functioning principle and expansion of the nickel-zinc battery. The active material for nickel zinc batteries is a good approach to refining the life cycle of the nickel zinc battery. This chapter also includes different types of active material for a better life cycle in nickel zinc battery. The applications of nickel-zinc battery are also discussed.
xvi Preface
Key Features
• Coverage on basic research and application approaches
• Explores challenges and future directions of Zn-based batteries
• Elaborates extensive properties of Zn batteries electrodes for future use
Editors
Rajender Boddula
Inamuddin
Abdullah M. Asiri
Carbon Nanomaterials for Zn-Ion Batteries
Prasun Banerjee1*, Adolfo Franco Jr2, Rajender Boddula3, K. Chandra Babu Naidu1 and Ramyakrishna Pothu4
1Department of Physics, Gandhi Institute of Technology and Management (GITAM) University, Bangalore, India
2Institute of Physics, Federal University of Goiás, Goiânia, Brazil
3CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, China
4College of Chemistry and Chemical Engineering, Hunan University, Changsha, China
Abstract
The development of the zinc-ion battery (ZB) hindered due to the problem associated with the suitability of its design especially on the catalyst and electrodes parts. Modified surface of carbon can enhance oxygen reduction reaction significantly for the catalytic performances. An ultimate design of ZBs should contain proper synthesis along with a precursor-like nitrogen with carbon-metal support for enhanced performances of ZBs. Electrodes formed with N-doped carbon fiber network with Co4N NPs not only provide high current density but also flexibility to ZBs. The ORR of ZBs can also be increased by using the N-doped carbon nanofiber (NCN). The enhancement of OER/ORR activity has been observed by coupling NiCo2S4 nanocrystals with nitrogen-doped carbon nanotubes (N-CNT/ NiCo2S4) for electrocatalyst applications in ZBs. P and S co-doped C3N4 sponge with C nanocrystal (P-S-CNS) demonstrated good OER and ORR activity. The OER and ORR performance can also be enhanced with the use of carbon nanosheets because of its greater surface area. The morphology and the porous structure in the N-rGO/NC cathode surface OER and ORR activity in ZBs.
The demand of storage energy especially without depending much on fossil fuels has been accelerated recent years with the progress in the battery field technologies [1–7]. The use of lithium undoubtedly makes it the leader in this sector. But, for the sake of electric vehicles (EVs), the use of lithium increase the cost many folds which is one of the reasons of unpopularity of EVs in the consumer vehicle market [8, 9]. In these sense, zinc, the 4th abundant metal in the world, can help to increase the popularity of the EVs by diminishing the cost the vehicles [10]. Theoretically, the zinc battery (ZB) possesses five times the energy density with respect to the lithium batteries. Hence, they are much more superior to that of its lithium counterpart both theoretically as well as economically. Despite of all this the advantages of ZB technology, its development highly hindered due to the problem associated with the suitability of its design especially on the catalyst and electrodes parts [11]. Modified surface of carbon can enhance oxygen reduction reaction significantly for the catalytic performances [12]. Hence, an ultimate design should contain proper synthesis along with a precursor-like nitrogen with carbon-metal support for enhanced performances of ZBs.
Electrodes formed with N-doped carbon fiber network with Co4N NPs shown in Figure 1.1 [13]. Meng et al. observed enhanced catalytic performances of CN/CFN/CC as an electrode in ZBs [13]. The following design not only provides 1 mA cm−2 current density but also flexible nature to ZBs in contrast to the conventional metal electrodes. The design can withstand 408 cycles with 1.09-V discharge-charge gap at 50 mA per cm2 with 20 h of retention of current density. Moreover, the flexible nature of the ZBs makes it a perfect power source for a wide range of wearable portable devices.
1.3 N-Doping of Carbon Nanofibers
The ORR of ZBs can enhance with the N-doped carbon nanofiber (NCN) as shown in Figure 1.2 [14]. Here, large surface area as well as the exposure of the NCNs increased the ORR activity. The use of NCNs can surpass the peak power density of available platinum/carbon catalyst of magnitude 192 mW cm−2 to by using NCNs in ZBs with a new magnitude of 194 mW cm−2 [14].
Carbon Nanomaterials for Zn-Ion Batteries 3
Figure 1.1 (a) Steps of Synthesis, (b)–(d) SEM images, (e) XRD, (f) TEM images and (g) EDS of CN/CFN/CC electrodes. Reprint with the permission from Reference [13]. Copyright 2016, ACS.
19.1µgPt/cm2
350 E (V vs Zn )
Figure 1.2 (a) ZB, (b) division of air electrode, (c) polarization graph, and (d) power density graph. Reprint with the permission from Reference [14]. Copyright 2013, Elsevier.
Moreover, the superiority of NCNs can also helps to achieve better electron numbers and hydrogen peroxide yields than that of the platinum/carbon catalyst.
1.4 NiCo2S4 on Nitrogen-Doped Carbon Nanotubes
The enhancement of OER/ORR activity has been observed by Han et al. by coupling NiCo2S4 nanocrystals with nitrogen-doped carbon nanotubes (N-CNT/NiCo2S4) for electrocatalyst applications in ZBs [15]. The
NiC02S1/N-CNT
NiC02S1/CNT
bare NiC02S1
roxide percentage Po tential (V versus RHE)
NiC02S1/N-CNT
NiC02S1/CNT bare NiC02S1 Pt/C Pt/C (60&109)
NiC02S1/CNT (59&115) bare NiC02S1 (63&116)
NiC02S1/N-CNT (56&111)
Log I (mA cm–2)
NiC02S1/CNT
NiC02S1/N-CNT
bare NiC02S1 Pt/C
NiC02S1/N-CNT
NiC02S1/CNT bare NiC02S1 Pt/C
w–10 (read–10 cm12)
Scan rate (mV s–1)
Figure 1.3 (a) Cyclic and (b) Linear voltammograms, (c) peroxide (solid) and no. of electrons (dotted), (d) K-L graph, (e) Tafel graph, (f) current densities of NiCo2S4, CNT/NiCo2S4, and N-CNT/NiCo2S4. Reprint with the permission from Reference [15]. Copyright 2017, Elsevier.
Carbon Nanomaterials for Zn-Ion Batteries 5
reversibility, stability, and bifunctional activity as shown in Figure 1.3 were up to the level of well-known metal catalysts performances. More positive cathode potential has been observed for N-CNT/NiCo2S4 in compression to its counterpart. Hence, this new design with carbon composites along with chalcogenides enables better performances for the ZBs.
1.5 3D Phosphorous and Sulfur Co-Doped C3N4 Sponge With C Nanocrystal
P and S co-doped C3N4 sponge with C nanocrystal (P-S-CNS) demonstrated good OER at 10 mA per cm2 current density with 1.56 V. The ORR activity also enhanced up to 7 mA cm−2 with 1-V potential [16]. Figure 1.4 also showed that the power density with the use of P-S-CNS in ZBs can reach up to 200 mW per cm2 at 200 mA per cm2 current density. Not only that, it can provide emf of 1.5 V at a specific capacitance of around 830 mAh per g1. The energy density also can reach up to 970 Wh per kg1 at 5 mA per cm2 current density. The reversibility and stability also enhances up to 500 cycles. Hence, the use of P-S-CNS in place of precious metals indeed demonstrates a cleaner and greener way of storage devices with respect to the conventional batteries.
Figure 1.4 (a) ZBs; (b) Power density; (c) Galvanostatic discharge graphs; (d) Specific capacity; (e) Stability; (f) Simple demonstration with P-S-CNS. Reprint with the permission from Reference [16]. Copyright 2016, ACS.
1.6 2D Carbon Nanosheets
The larger surface area of 1,050 m2 per g of the nanosheets of carbon indeed makes it suitable for the application of the ZBs [17]. Figure 1.5 shows the SEM images of the 2D structure of the nanosheets. The OER and ORR performance can be enhanced with the use of carbon nanosheets because of its greater surface area which increase the oxygen absorption and enhance the catalytic activities in many folds. The platinum/carbon galvanic discharge voltage 1.2 V of current density of 5 mA per cm2 can be achievable using the carbon nanosheets in ZBs. Hence, the competitive performances with the low cost of production indeed make it a suitable choice to use in the ZBs.
1.7 N-Doped Graphene Oxide With NiCo2O4
Graphene oxide with N-doped along with NiCo2O4 (N-rGO/NC) can be used as another stable cathode electrode for the ZBs applications [18]. The flower-like structure of the N-rGO/NC is shown in Figure 1.6. The flowerlike structure helps to obtain 4-V plateau in the charge profile whereas
Figure 1.5 SEM images of 2D carbon nanosheets. Reprint with the permission from Reference [17]. Copyright 2015, RSC.
1.6 SEM, TEM, and XRD N-rGO/NC. Reprint with the permission from Reference [18]. Copyright 2017, RSC.
the plateau is situated around 2.6 V for the discharge profile. The capacity of the ZBs with the use of N-rGO/NC cathode can reach up to 7,000 mAh g−1 till 35 h. The morphology and the porous structure in the N-rGO/NC cathode surface help better flow of oxygen which enhances the OER and ORR activity.
1.8 Conclusions
In summary, the development of the zinc-ion battery (ZB) hindered due to the problem associated with the suitability of its design especially on
Figure
the catalyst and electrodes parts. Modified surface of carbon can enhance oxygen reduction reaction significantly for the catalytic performances. An ultimate design of ZBs should contain proper synthesis along with a precursor-like nitrogen with carbon-metal support for enhanced performances of ZBs. For example, electrodes formed with N-doped carbon fiber network with Co4N NPs not only provide 1 mA cm−2 current density but also flexibility to ZBs. The ORR of ZBs can also increase with N-doped carbon nanofiber (NCN). The enhancement of OER/ORR activity has been observed by coupling NiCo2S4 nanocrystals with nitrogen-doped carbon nanotubes (N-CNT/NiCo2S4) for electrocatalyst applications in ZBs.
P and S co-doped C3N4 sponge with C nanocrystal (P-S-CNS) demonstrated good OER 10 mA per cm2 current density with 1.56 V. The ORR activity also enhanced up to 7 mA cm−2 with 1-V potential. The OER and ORR performance can be enhanced with the use of carbon nanosheets because of its greater surface area which increase the oxygen absorption and enhance the catalytic activities in many folds. The morphology and the porous structure in the N-rGO/NC cathode surface help better flow of oxygen which enhances the OER and ORR activity in the ZBs.
Acknowledgements
The author acknowledges UGC, India, for the start-up financial grant no. 30-457/2018(BSR). We also acknowledge the support provided to A. Franco Jr. by CNPq, Brazil, with grant no. 307557/2015-4.
References
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Carbon Nanomaterials for Zn-Ion Batteries 9
6. Yoo, H.D., Markevich, E., Salitra, G., Sharon, D., Aurbach, D., On the challenge of developing advanced technologies for electrochemical energy storage and conversion. Mater. Today, 17, 3, 110–121, 2014.
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13. Meng, F., Zhong, H., Bao, D., Yan, J., Zhang, X., In situ coupling of strung Co4N and intertwined N–C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn–air batteries. J. Am. Chem. Soc., 138, 32, 10226–10231, 2016.
14. Park, G.S., Lee, J.S., Kim, S.T., Park, S., Cho, J., Porous nitrogen doped carbon fiber with churros morphology derived from electrospun bicomponent polymer as highly efficient electrocatalyst for Zn–air batteries. J. Power Sources, 243, 267–273, 2013.
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2
Construction, Working, and Applications of Different Zn-Based Batteries
G. Ranjith Kumar1, K. Chandra Babu Naidu2*, D. Baba Basha3, D. Prakash Babu1, M.S.S.R.K.N. Sarma2, Ramyakrishna Pothu4 and Rajender Boddula5
1Department of Physics, School of Applied Sciences, REVA University, Bangalore, India
2Department of Physics, GITAM Deemed to be University, Bangalore, India
3College of Computer and Information Sciences, Majmaah University Al’Majmaah, Al’Majmaah, Saudi Arabia
4College of Chemistry and Chemical Engineering, Hunan University, Changsha, China
5CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, China
Abstract
Zn batteries are preferred among all other metal batteries because of their salient features like great safety, low cost, environmental friendliness, and, above all, high theoretical energy density. This chapter is aimed at the construction, working, and applications of zinc-based batteries. In view of this, the basic anode, cathode, and electrolyte materials for these batteries are discussed. In case of zinc-carbon batteries, the MnO2/CO2 mixture, an electrolyte and carbon is used as cathode. Similarly for zinc-cerium batteries and zinc-bromine batteries, the redox reaction mechanism, electrode, and electrolytes are briefly explained. Moreover, the discussion is made on how best the present zinc-based batteries rather than other batteries for electrical energy storage applications.
Energy is an important concern for us in all aspects of modern lifestyle [1]. Current research in energy focuses on development of novel materials for energy storage, energy harvest, and utilization of renewable energy [1]. Lithium-ion batteries are the widely adopted energy storage solution in the recent times. They are widely used in portable electronics including mobile phones and laptops and also in electric vehicles. However, Li-ion batteries have their own limitations of blemished safety, insufficient energy density, and durability, which is a big setback for the adoption of Li-ion batteries in long-range electric vehicles [1]. To overcome these setbacks, post Li-ion battery technologies have been proposed and they include Na-ion, Li-S, and metal-air battery packs. Among them, metal-air battery packs are considered as the best bet based on their high proposed energy density and its capacity to utilize atmospheric oxygen as fuel [1]. Among the available metalair battery packs, Li-O batteries are extensively researched owing to their good specific energy density which is about 5,200 Wh kg–1 [2]. Though, their safety, cost issues, and rechargeability are hurdles to them to be commercialized. Due to these unsolved issues in Li-O batteries, researches shift their paradigm to rechargeable Zn-air batteries recently [1]. Availability of zinc is several times more when compared to the availability of lithium. Several types of primary batteries use zinc as preferred electrode material. In 1930s, primary Zn-air batteries were first introduced and commercialized [1]. Zn-air batteries are preferred among all other metal-air batteries because of their salient features like great safety, low cost, environmental friendliness, and, above all, high theoretical energy density [1].
Zinc electrode-based batteries have added advantages like high discharge and lightweight [3–5]. Even though companies like Evercel, Fluidic Energy, Z-Power, EOS, Zinc Five, ZnR Batteries, ZAF, Zinium, etc., have patented and commercialized zinc-based battery solutions, only Fluidic Energy is currently producing reversible Zn-air technology. This implies zinc electrode still suffers durability, i.e., limited life cycle [6]. This durability limitation arises due to different technical issues like corrosion of zinc, zinc electrode shape change, dendrite formation, and high dissolution rate of zinc in electrolytes [7, 8]. Limitations also arise from the constancy and bi-functional air electrode performance that needs significant cell voltage changes support during the cycle [1].
At the time of charging, the non-homogeneous re-deposition of zinc occurs leading to huge current per unit area (current density). The irregular rearrangement of zinc cations within the vicinity of electrode allows dendritic diffusion-controlled deposition and changes in the shape of the
electrode after introducing the electrolyte in the form of a solution; “Fluidic Energy” solved these technical disadvantages, along with other engineering advancements. In the last decade, many efforts were modify to develop and optimize zinc electrodes. These include addition of additives either to the electrolyte and/or to the electrode itself [3, 5–18]. Unfortunately, these additives reduce the quantity related to the Zn-ions over electrode, and hence, it leads to poor specific energy of the battery and its poor performance [9, 12]. Consequently, different strategies must be adopted to limit the quantity related to Zn and it disperses within the electrolyte. Conversely, zinc electrode modifications have been tried by adding conductive organic and inorganic binders and alternative binders [19–27]. The common aim is to increase the reversibility and recharge life cycle of the battery pack. Zhu et al. [27] reported the reduced dendrite formation by coating zinc electrodes with neodymium, neodymium hydroxide, and lanthanum hydroxide, he also confirmed [1]. Vastalarani et al. [23] demonstrated corrosion reversibility and zinc electrode protection by depositing conducting polymer electrode surface. However, Miyazaki et al. [25] reported reduced dendrite growth on the electrodes using anion-exchange ionomers. Zhu et al. [24] tried coating on zinc electrodes with different ionomer films and observed an overall decrease of dissolved discharge products of zinc into the electrolyte. Similarly, Stock et al. [28] reported the way of enhancing the cycle life of Zn batteries using the anion interchange method.
2.2 History
A battery is consists of two metals/compounds with different chemical potentials divided by a porous insulating material. The energy stored in the atoms or bonds is then transferred to the moving electrons which powers the external device connected to it. Transfer of ions from one electrode to other during the reaction happens through the electrolyte (e.g., salt and water). Anode loses electrons, and the cathode accepts the electrons [1]. Sometimes, compromise has to be made on the battery specifications based on the requested working circumstances of battery and also in order to satisfy the demand in market. For instance, implementation of different strategies to improve life cycle of battery may affect its performance [1–3]. The first rechargeable Zn-air battery was made by Miro Zoric in 1996 in order to power first AC-based drive trains developed by him. In Singapore, small- and mid-sized buses started to use zinc-air batteries. In 1997, mass production facilities for Zn-air batteries was setup. These batteries gave better specific energy and energy density, when compared to lead-acid batteries which were common at that time.
2.3 Types of Batteries
There are two types of batteries: they are primary and secondary batteries.
2.3.1 Primary Battery
Primary batteries (also called primary cells) (Figure 2.1) are capable of producing current right after their assembly. They are widely used in low current consuming portable devices, are not used continuously, or are used when a regular power supply is far away, such as in communication circuits and alarm where the electricity is available only temporarily. Because of non-reversible chemical reactions and non-reversal of active materials to their original forms, disposable primary cells cannot be recharged. Primary batteries strictly should not be recharged, because of the risk of explosion [29]. Primary batteries have higher energy density than rechargeable batteries [30]; primary batteries are preferred under applications demanding high-drain with loads less than 75 Ω. Zinc-carbon batteries and alkaline batteries are commonly used disposable batteries.
2.3.2 Secondary Battery
Before their first use, secondary batteries (also called rechargeable batteries) (Figure 2.2) should be charged; they contain active materials in the discharged state. Applying electric current, these battery gets (re)charged; electric current reverses the chemical reaction that occurred because of discharge. Devices used to provide the appropriate current and voltages are called chargers. Lead-acid battery is the first rechargeable batteries that Negative terminal Gasket Positive electrode (Manganese dioxide) Negative electrode (Zinc)
Figure 2.1 Structure of primary battery.
are commonly used in boating and automotive systems. Rechargeable battery contains a liquid electrolyte in an enclosure that is loosely packed; the battery must be kept upright in a well-ventilated area for safe dispersal of hydrogen gas evolved when overcharged. The lead-acid battery is comparatively bulky for quantity of electricity it can store. Owing to its affordable manufacturing cost and their ability to handle large amount of surge current, they are commonly used in places where its capacity dominates over their weight and handling issues [31]. Application of them include modern EV that delivers a peak current of 450 A. Zn-air batteries and Zn-air fuel cells are batteries powered by oxidizing zinc with atmospheric oxygen. They are less expensive to produce and possess high energy densities. They come in different sizes ranging from the size of a shirt button to power hearing aids, large batteries to power cinema cameras to very large batteries to power EVs.
While discharging, the anode becomes porous due to the accumulation of zinc particles on the electrolyte. At the cathode, atmospheric oxygen reacts at the cathode forming hydroxyl ions. These hydroxyl ions diffuse within Zn light liquid leading to Zn(OH)2−4 formation. The electrons (e ) are released in this process and they travel to the cathode. The (Zn(OH)2−4) decays into ZnO and water molecules diffuse to the electrolyte. At the cathode, the hydroxyl and water from the anode get recycled; therefore, water is not used up. Theoretically, this reaction produces 1.65 volts; however, practically only 1.35–1.4 V is available. Zn-air batteries are the hybrid of fuel cells and batteries: zinc is the fuel; rate of the reaction is controlled by varying the airflow. Oxidized zinc/electrolyte paste can be replaced with
Cathode
Figure 2.2 Structure of secondary battery.
16 Zinc Batteries
the fresh one. Possible future deployment of this battery include its use as a utility-scale energy storage system and as an EV battery. Recently, Zn-air batteries are receiving great amount of attention. They have a high storage capacity, low toxicity, and low cost, and they are competitive with modern batteries like Li-ion and NiMH. Zn-air batteries oxidize by taking atmospheric oxygen. There are four components in a Zn-air battery, i.e., zinc anode, air cathode, electrolyte, and separator (Figure 2.3).
Recently, lot of attention is devoted on electric recharging Zn-air battery packs. This chapter addresses the challenges in the development of electrically rechargeable Zn-air batteries with alkaline electrolytes and advancement from materials to methods aiming at tackling these technical limitations. Mechanically rechargeable batteries were investigated for decades for their possible applications in EVs. Few methods adopt a large Zn-air battery for maintaining electric charge at high discharge rate. These batteries are capable of handling load surge produced while accelerating the vehicle. These packs use zinc granules that are used as reactant. Battery packs installed in EVs can be refurbished by interchanging Zn and electrolyte material with new ones near maintenance station. Within Zn-air battery, simultaneous addition of new zinc and removal of used zinc (ZnO) is done.
Electrically rechargeable Zn-air batteries need to control precipitation of zinc from the electrolyte. Challenges include limited solubility of Zn in electrolytes, non-uniform zinc dissolution, and dendrite formation. A bi-functional air cathode is capable of electrically reversing the reaction and
